Divalent cation removal from rich monoethylene glycol (meg) feed streams by ion exchange

ABSTRACT

A system and process for removing divalent cations from a rich MEG feed stream is presented. An ion exchange bed containing a cation exchange resin adsorbs the divalent cations in the rich MEG feed stream as it flows through the ion exchange bed. After the divalent ions have been removed, the feed stream flows through a flash separator and a distillation column to reclaim MEG. Alternatively, the feed stream flows through a distillation column to regenerate MEG. The spent cation exchange resin may be regenerated in place using a regeneration brine comprised of sodium chloride and water. After use, the regeneration brine may be disposed as waste or recycled to the brine storage tank and re-used to regenerate the cation exchange resin.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. patentapplication Ser. No. 15/254,125 filed Sep. 1, 2016, which is acontinuation of Ser. No. 13/593,734, filed Aug. 24, 2012, now U.S. Pat.No. 9,433,875, issued Sep. 6, 2016. All cross-referenced applicationslisted herein are incorporated by reference in their entirety.

BACKGROUND OF THE INVENTION

This invention relates to systems and processes designed to treatmonoethylene glycol (MEG) used in the oil and gas industry, especiallyin offshore locations, to control the formation of hydrates. Moreparticularly, the invention relates to MEG reclamation or regenerationprocesses that are designed to remove divalent cations from a rich MEGfeed stream.

In the oil and gas industry, lean (dry) MEG is mixed with the water in aproduced stream to control the formation of hydrates within the stream.The now rich (wet) MEG is, in turn, dried 25 by way of a MEG reclamationor MEG regeneration process so that the MEG can be re-used in hydratecontrol. The lean MEG cannot be recovered by simply distilling the richMEG and water in conditions of high salt concentration because the richMEG is loaded with dissolved salt ions from the produced water. Sodiumchloride is commonly the most concentrated salt in the produced water,but it may also contain dissolved divalent salts of magnesium, calcium,strontium, and barium. If these divalent cations are not removed orcontrolled at a low concentration, their high solubility in MEG willalter the physical properties of the MEG, eventually leading to failureof the reclamation or regeneration process.

In the current process for separating divalent cations from the rich MEGfeed stream, the ions react with carbonate or hydroxide anions to forminsoluble salt crystals, which are then removed from the feed stream.This process generally requires the addition of caustic and acid tocompletely remove the divalent cations and to neutralize the feed streambefore it enters the MEG reclamation or MEG regeneration process.

The time and temperature of the current separation process must bestrictly controlled. In addition, the process requires large andexpensive equipment, as well as additional chemicals that are notinherently available as part of the MEG reclamation or MEG regenerationprocess. These chemicals must be obtained from outside sources which canbe very expensive, particularly when delivered to offshore platforms inremote parts of the world. The chemicals may also be a safety concern,require specialized handling and storage, and increase training,reporting, and record.keeping requirements. The current separationprocess also produces a carbonate salt in the form of a solid or slurrymaterial that is generally insoluble and requires disposal as a waste.Proper disposal of this material can be expensive, time-consuming, andlabor-intensive. Disposal is even more difficult in offshoreapplications where temporary storage space and transportation to anapproved disposal site are not readily available.

A need exists for systems and processes for removing divalent cationsfrom rich MEG feed streams in order to improve the efficiency of the MEGreclamation or MEG regeneration process and to prevent the accumulationof salts inside the process equipment. A need also exists for systemsand processes that are less expensive, easier to operate, do not requirelarge amounts of space or additional chemicals, and facilitate thedisposal of process waste streams.

SUMMARY OF THE INVENTION

A system for removing divalent cations from a rich MEG feed stream ispresented. The system includes an ion exchange bed containing a cationexchange resin that adsorbs the divalent cations in the rich MEG feedstream as it flows through the bed. After the divalent cations have beenremoved, the feed stream flows through a flash separator and adistillation column to reclaim MEG. Alternatively, the feed stream flowsthrough a distillation column to regenerate MEG. The spent cationexchange resin may be regenerated, without removing it from the ionexchange bed, using a regeneration brine. The regeneration brine may becomprised of distilled water that is produced during the MEG reclamationor MEG regeneration process. The regeneration brine may also becomprised of sodium chloride that is produced during the MEG reclamationprocess. After use, the regeneration brine may be disposed of as wasteor recycled to the brine storage tank and re-used to regenerate thecation exchange resin.

A process for removing divalent cations from a rich MEG feed stream isalso presented. The process includes the steps of providing an ionexchange bed containing a cation exchange resin and passing the rich MEGfeed stream through the bed so that the divalent cations are adsorbed tothe resin. The process may also include the step of MEG reclamation orMEG regeneration. A regeneration brine may be used to regenerate thespent cation exchange resin without removing it from the ion exchangebed. The regeneration brine may be comprised of distilled water producedduring the MEG reclamation or MEG regeneration process. The regenerationbrine may also be comprised of sodium chloride that is produced duringthe MEG reclamation process. After use, the regeneration brine may bedisposed of as waste or recycled to the brine storage tank and re-usedto regenerate the cation exchange resin.

The objects of this invention are to (1) provide a more efficientprocess to remove divalent cations contained in a rich MEG feed streambefore the stream enters a MEG reclamation or MEG regeneration process;(2) simplify the removal process by eliminating required conditions fortime and temperature; (3) reduce the volume, footprint, and cost of theprocessing equipment typically required to remove divalent cations fromthe rich MEG feed stream; (4) provide a renewable or reusable bed fordivalent cation removal; (5) provide a process for physical separationof the divalent cations from the rich MEG feed stream, thus eliminatingthe need for additional chemicals; and (6) facilitate the disposal ofwaste streams.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 presents an embodiment of a process for removing divalent cationsfrom a rich MEG feed stream as part of a MEG reclamation process,practiced according to this invention.

FIG. 2 presents an embodiment of a process for removing divalent cationsfrom a rich MEG feed stream as part of a MEG regeneration process,practiced according to this invention.

ELEMENTS AND NUMBERING USED IN THE DRAWINGS AND THE DETAILED DESCRIPTION

-   10 Divalent cation removal process-   15 Rich MEG feed stream-   20 Ion exchange bed-   25 Rich MEG stream with the majority of divalent cations removed-   30 Flash separator-   35 Sodium chloride waste stream-   40 Vaporized water and MEG stream-   45 Distillation column-   150 Lean MEG-   55 Distilled water-   60 Brine storage tank-   65 Regeneration brine-   70 Waste stream of sodium chloride and calcium chloride brine-   80 Sodium chloride-   85 Rich MEG feed stream-   90 Rich MEG stream with the majority of divalent cations removed-   95 Vaporized water

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

An ion exchange process may be used to remove divalent cations from therich MEG feed stream before the feed stream enters the MEG reclamationprocess, as shown in FIG. 1, or the MEG regeneration process, as shownin FIG. 2. This ion exchange process is different than conventionalwater treatment because the rich MEG feed stream is more viscous thanwater and 25 interacts differently with the ion exchange resins. Inaddition, the ion exchange resins of the present invention are subjectto higher concentrations of sodium and calcium than would generally befound in water treatment systems.

As shown in FIG. 1, a preferred embodiment of a divalent cation removalprocess 10A practiced according to this invention begins with the richMEG feed stream 15, which is a mixture of produced water and MEG. Therich MEG feed stream 15 is routed to a divalent cation removal stepcomprised of dual ion exchange beds 20 which contain a strong cationexchange resin in the sodium form and alternate between adsorption andregeneration phases. In the adsorption phase, the resin removes divalentcations from the rich MEG feed stream 15 by adsorbing the divalentcations from the produced water and displacing the sodium cations.Although two ion exchange beds 20 are shown in FIG. 1, the ion exchangeprocess may use more than two beds or a single bed.

The rich MEG stream with the majority of divalent cations removed 25then exits the ion exchange beds 20 and flows to the MEG reclamationprocess. The MEG reclamation process begins in a flash separator 30,where the pressure is reduced in order to separate salts from the richMEG and water. A sodium chloride waste stream 35 exits the bottom end ofthe flash separator 30, while the vaporized water and MEG stream 40exits the top end and flows to the distillation column 45. Thedistillation column 45 uses partial condensation to separate the waterand MEG components of the vaporized water and MEG stream 40. Lean MEG 50exits the bottom end of the distillation column 45 and distilled water55 is discharged from the top end of the distillation column 45. Aftermeeting necessary quality requirements, the distilled water 55 may bedischarged as waste or recycled to the brine storage tank 60.

Regeneration of the ion exchange beds 20 may be accomplished with watercontaining large amounts of a salt. In the embodiment described in FIG.1, the sodium chloride waste stream 35 from the flash separator 30 iscombined with distilled water 55 from the distillation column 45 in thebrine storage tank 60 to form regeneration brine 65. At the beginning ofthe regeneration process, one of the ion exchange beds 20 is takenoff-line by diverting the flow of the rich MEG feed stream 15 from thatbed 20 to the alternate bed 20. A stream of regeneration brine 65 fromthe brine storage tank 60 is then routed through the off-line ionexchange bed 20 in a direction opposite that of the flow of the rich MEGfeed stream 15. Divalent cations that have been adsorbed to the cationexchange resins inside the ion exchange bed 20 leave the resins andenter the stream of regeneration brine 65, forming a waste stream ofsodium chloride and calcium chloride brine 70 that exits from the top ofthe ion exchange bed 20. The waste stream of sodium chloride and calciumchloride brine 70 can be disposed of as waste or re-used to regeneratethe ion exchange beds 20.

As shown in FIG. 2, an ion exchange process may also be used toregenerate MEG by removing divalent cations from the rich MEG feedstream. This process may be used in applications where the producedwater is relatively free of salts and the purity standards for MEG areless stringent. However, the MEG may contain divalent cations at aconcentration that would cause equipment and scaling issues. Removingthese ions protects downstream equipment and extends the useful life ofthe MEG.

A preferred embodiment of a divalent cation removal process 10Bpracticed according to this invention begins with a rich MEG feed stream85, which is routed to a divalent cation removal step. The divalentcation removal step is comprised of dual ion exchange beds 20 whichcontain a strong cation exchange resin in the sodium form and alternatebetween adsorption and regeneration phases. In the adsorption phase, theresin removes divalent cations from the feed stream 85 by adsorbing thedivalent cations from the produced water and displacing the sodiumcations. Although two ion exchange beds 20 are shown in FIG. 2, the ionexchange process may use more than two beds or a single bed.

The rich MEG stream with the majority of divalent cations removed 90then exits the ion exchange beds 20 and flows to a distillation column45, which separates the water from the lean MEG. Lean MEG 50 exits thebottom end of the distillation column 45, while the vaporized water 95exits the top end. After the vaporized water 95 cools, it may bedischarged as waste or recycled to the brine storage tank 60.

Regeneration of the ion exchange beds 20 may be accomplished with watercontaining large amounts of a salt. In the embodiment described in FIG.2, sodium chloride 80 from an external source is combined with the water95 from the distillation column 45 in the brine storage tank 60 to formregeneration brine 65. At the beginning of the regeneration process, oneof the ion exchange beds 20 is taken off-line by diverting the flow ofthe rich MEG feed stream 85 from that bed 20 to the alternate bed 20. Astream of regeneration brine 65 from the brine storage tank 60 is thenrouted through the off-line ion exchange bed 20 in a direction oppositethat of the flow of the feed stream 85. Divalent cations that have beenadsorbed to the ion exchange resins inside the ion exchange bed 20 leavethe resins and enter the stream of regeneration brine 65, forming awaste stream of sodium chloride and calcium chloride brine 70 that exitsfrom the top of the ion exchange bed 20. The waste stream of sodiumchloride and calcium chloride brine 70 can be disposed of as waste orre-used to regenerate the ion exchange beds 20.

The present invention allows the MEG to remain in service for a longerperiod of time before the concentration of divalent cations increases toa level that could cause scaling or corrosion of the equipment. Anotheradvantage of the present invention is that distilled water, which isproduced during MEG reclamation and MEG regeneration and conventionallymanaged as a waste material, is recycled to form regeneration brine.Sodium chloride produced during MEG reclamation can also be recycled toform regeneration brine. Another advantage is that the waste stream ofsodium chloride and calcium chloride brine from regeneration of the ionexchange beds contains only the salts that were originally present inthe produced water. As a result, this waste stream can be discharged, ifthe appropriate water quality standards are met, to the marineenvironment or an injection well. This waste stream may also be recycledthrough the regeneration process for the cation exchange resin in theion exchange beds until the concentration of divalent cations increasesto a level that impairs regeneration of the resin.

While preferred embodiments of a system and process for removingdivalent cations from a rich MEG feed stream have been described indetail, a person of ordinary skill in the art understands that certainchanges can be made in the arrangement of process steps and type ofcomponents used in the system and process without departing from thescope of the following claims.

We claim:
 1. A process for removing divalent cations from a feed streamcontaining water and monoethylene glycol (MEG), the process comprising:passing the feed stream through an ion exchange bed containing a cationexchange resin, wherein the divalent cations are adsorbed by the cationexchange resin to form an effluent stream; and passing the effluentstream from the ion exchange bed through a distillation column to yieldMEG and distilled water.
 2. The process of claim 1, further comprisingregenerating the cation exchange resin by passing a regeneration brinethrough the cation exchange resin.
 3. The process of claim 2, whereinthe regeneration brine comprises water from the distillation column. 4.The process of claim 3, wherein the regeneration brine is stored in abrine storage tank.
 5. The process of claim 4, wherein the feed streamis passed through the ion exchange bed in a first direction, and theregeneration brine is routed from the brine storage tank to the ionexchange bed in a second direction opposite from the first direction. 6.The process of claim 5, wherein the regeneration brine is formed bymixing sodium chloride from an external source with the water from thedistillation column.
 7. The process of claim 6, wherein the regenerationbrine is re-used to regenerate the ion exchange bed.
 8. A process forremoving divalent cations from a feed stream containing water andmonoethylene glycol (MEG), the process comprising: passing the feedstream in a first direction through an ion exchange bed containing acation exchange resin, wherein the divalent cations are adsorbed by thecation exchange resin to form an effluent stream; passing the effluentstream from the ion exchange bed through a distillation column to yieldMEG and distilled water; and regenerating the cation exchange resin bypassing a regeneration brine through the ion exchange bed in a seconddirection opposite from the first direction.
 9. The process of claim 8,wherein the regeneration brine is formed in a regeneration brine tank bymixing sodium chloride from an external source with water from thedistillation column.
 10. The process of claim 8, wherein theregeneration brine is sourced from a regeneration brine tank and isre-used.
 11. The process of claim 8, wherein the regeneration brinecomprises sodium chloride sourced from MEG reclamation and water fromthe distillation column.
 12. The process of claim 8, wherein theregenerating forms a waste stream containing only salts originallypresent in the feed stream.
 13. The process of claim 12, wherein theregeneration brine is formed using water obtained from the distillationcolumn.
 14. The process of claim 12, wherein the waste stream is used asa regeneration brine.
 15. The process of claim 8, wherein vaporizedwater from the distillation column is cooled and routed to aregeneration brine tank, and sodium chloride is added to theregeneration brine tank to form the regeneration brine.
 16. The processof claim 15, wherein the sodium chloride is obtained from an externalsource.
 17. The process of claim 15, wherein the sodium chloride isobtained from a waste stream of the regeneration operation.
 18. Aprocess for removing divalent cations from a feed stream containingwater and monoethylene glycol (MEG), the process comprising: passing thefeed stream in a first direction through an ion exchange bed containinga cation exchange resin, wherein the divalent cations are adsorbed bythe cation exchange resin to form an effluent stream; passing theeffluent stream from the ion exchange bed through a distillation columnto yield MEG and distilled water; and regenerating the cation exchangeresin by passing a regeneration brine, formed using water from thedistillation column, from a regeneration brine tank through the ionexchange bed in a second direction opposite from the first direction.19. The process of claim 18, wherein sodium chloride obtained as a wastestream from the regeneration process is added to the regeneration brinetank to make the regeneration brine.
 20. The process of claim 19,wherein sodium chloride from an external source is also added to theregeneration brine tank to make the regeneration brine.